EP3483530B1 - Refrigeration purge system - Google Patents
Refrigeration purge system Download PDFInfo
- Publication number
- EP3483530B1 EP3483530B1 EP18205247.2A EP18205247A EP3483530B1 EP 3483530 B1 EP3483530 B1 EP 3483530B1 EP 18205247 A EP18205247 A EP 18205247A EP 3483530 B1 EP3483530 B1 EP 3483530B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- membrane
- purge
- refrigeration system
- purge gas
- circulation loop
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000010926 purge Methods 0.000 title claims description 92
- 238000005057 refrigeration Methods 0.000 title claims description 29
- 239000012528 membrane Substances 0.000 claims description 110
- 239000003507 refrigerant Substances 0.000 claims description 53
- 239000012530 fluid Substances 0.000 claims description 39
- 239000000356 contaminant Substances 0.000 claims description 33
- 239000013529 heat transfer fluid Substances 0.000 claims description 23
- 238000004891 communication Methods 0.000 claims description 20
- 238000012546 transfer Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000012466 permeate Substances 0.000 claims description 13
- 230000004044 response Effects 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 229910010272 inorganic material Inorganic materials 0.000 claims description 7
- 239000011147 inorganic material Substances 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000012465 retentate Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 51
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- 230000006835 compression Effects 0.000 description 12
- 238000007906 compression Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000012229 microporous material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 7
- 239000002135 nanosheet Substances 0.000 description 7
- 238000013517 stratification Methods 0.000 description 7
- 239000013110 organic ligand Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920005596 polymer binder Polymers 0.000 description 5
- 239000002491 polymer binding agent Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- -1 clays (e.g. Chemical compound 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013257 coordination network Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 239000004941 mixed matrix membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B49/00—Arrangement or mounting of control or safety devices
- F25B49/02—Arrangement or mounting of control or safety devices for compression type machines, plants or systems
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B43/00—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B43/00—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat
- F25B43/003—Filters
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B43/00—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat
- F25B43/04—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat for withdrawing non-condensible gases
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28G—CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS
- F28G9/00—Cleaning by flushing or washing, e.g. with chemical solvents
Definitions
- This disclosure relates generally to chiller systems used in air conditioning systems, and more particularly to a purge system for removing contaminants from a refrigeration system.
- Chiller systems such as those utilizing centrifugal compressors may include sections that operate below atmospheric pressure. As a result, leaks in the chiller system may draw air into the system, contaminating the refrigerant. This contamination degrades the performance of the chiller system.
- existing low pressure chillers include a purge unit to remove contamination.
- Existing purge units use a vapor compression cycle to separate contaminant gas from the refrigerant.
- Existing purge units are complicated and lose refrigerant in the process of removing contamination.
- Document US 5 044 166 A discloses a refrigeration system according to the preamble of claim 1
- the present invention provides a refrigeration system as in claim 1 and a method for operating a refrigeration system as in claim 12.
- a refrigeration system including a heat transfer fluid circulation loop configured to allow a refrigerant to circulate therethrough.
- a purge gas outlet is in operable communication with the heat transfer fluid circulation loop.
- the system also includes at least one gas permeable membrane having a first side in operable communication with the purge gas outlet and a second side.
- the membrane includes a porous inorganic material with pores of a size to allow passage of contaminants through the membrane and restrict passage of the refrigerant through the membrane.
- the system also includes a permeate outlet in operable communication with a second side of the membrane.
- the system further includes a prime mover operably coupled to the permeate outlet, and the prime mover is configured to move gas from the second side of the membrane to an exhaust port leading outside the fluid circulation loop.
- the heat transfer fluid circulation loop includes a compressor, a heat rejection heat exchanger, an expansion device, and a heat absorption heat exchanger, connected together in order by conduit, and the purge gas outlet is in operable communication with at least one of the heat rejection heat exchanger, the heat absorption heat exchanger and the membrane.
- the system further includes a retentate return conduit operably coupling the first side of the membrane to the fluid circulation loop.
- the prime mover is a vacuum pump
- the system further includes a purge gas collector operably coupled to the purge outlet and the membrane.
- the purge gas collector includes purge gas therein comprising refrigerant gas and contaminants, said purge gas in a stratified configuration with a higher concentration of refrigerant toward the purge outlet and a higher concentration of contaminants toward the membrane.
- system further includes a chiller coil disposed in the purge gas collector, the coil in operable communication with the fluid circulation loop.
- the system further includes a heat source, said heat source being in controllable thermal communication with at least one of the membrane and the purge gas collector.
- the system further includes a heat source in controllable thermal communication with either or both of the membrane or a purge gas collector between the purge outlet and the membrane.
- the membrane includes a ceramic.
- the at least one gas permeable membrane includes a plurality of gas permeable membranes; wherein the plurality of gas permeable membranes are arranged in serial or parallel communication.
- system further includes a second prime mover conduit to move permeate from the second side of the membrane to the first side of the membrane.
- the system further includes a filter or a vortex separator between the purge outlet and the membrane.
- system further includes a controller configured to operate fluid circulation loop in response to a cooling demand signal and to operate the prime mover in response to a determination of contaminants in the fluid circulation loop.
- a method of operating a refrigeration system including circulating a refrigerant through a vapor compression heat transfer fluid circulation loop in response to a cooling demand signal.
- the fluid circulation loop includes a heat rejection side of a first heat exchanger, an expansion device, and the heat absorption side of a second heat exchanger, connected together in order by conduit under conditions in which the refrigerant is at a pressure less than atmospheric pressure in at least a portion of the fluid circulation loop.
- Purge gas including contaminants is collected from a purge outlet in the fluid circulation loop and transferred across a permeable membrane with a prime mover.
- the membrane includes a porous inorganic material with pores of a size to allow passage of the contaminants through the membrane and restrict passage of the refrigerant through the membrane.
- the method further includes collecting the purge gas in a purge gas collector between the purge outlet and the membrane.
- the method includes stratifying purge gas in the purge gas collector with a higher concentration of refrigerant toward the purge outlet and a higher concentration of contaminants toward the membrane.
- the method further includes returning refrigerant from the first side of the membrane to the fluid circulation loop.
- the purge system receives gas comprising refrigerant gas and contaminants (e.g., nitrogen, oxygen, or water) from a refrigerant-containing refrigeration system such as shown in FIG. 12 through a purge connection 52 to a membrane separator 54 on a first side of a membrane 56.
- the contaminants may comprise a non-condensable gas such as components of atmospheric air (e.g., nitrogen, oxygen).
- a prime mover such as a vacuum pump 58 connected to the membrane separator 54 through connection 60 provides a driving force to pass the contaminant molecules through the membrane 56 and exit the system from a second side of the membrane 56 through an outlet 58.
- the prime mover may be in the fluid loop, e.g., a refrigerant pump or compressor. Refrigerant gas tends to remain on the first side of the membrane 56 and can return to the fluid circulation loop through connection 64.
- a controller 50 the operation of which is described in more detail below, is in operable communication with the refrigeration system components.
- the membrane 56 includes a porous inorganic material.
- porous inorganic materials can include ceramics such as metal oxides or metal silicates, more specifically aluminosilicates (e.g., Chabazite Framework (CHA) zeolite, Linde type A (LTA) zeolite, porous carbon, porous glass, clays (e.g., Montmorillonite, Halloysite).
- Porous inorganic materials can also include porous metals such as platinum and nickel.
- Hybrid inorganic-organic materials such as a metal organic framework (MOF) can also be used.
- Other materials can be present in the membrane such as a carrier in which a microporous material can be dispersed, which can be included for structural or process considerations.
- Metal organic framework materials are well-known in the art, and comprise metal ions or clusters of metal ions coordinated to organic ligands to form one-, two- or three-dimensional structures.
- a metal-organic framework can be characterized as a coordination network with organic ligands containing voids.
- the coordination network can be characterized as a coordination compound extending, through repeating coordination entities, in one dimension, but with cross-links between two or more individual chains, loops, or spiro-links, or a coordination compound extending through repeating coordination entities in two or three dimensions.
- Coordination compounds can include coordination polymers with repeating coordination entities extending in one, two, or three dimensions.
- organic ligands include but are not limited to bidentate carboxylates (e.g., oxalic acid, succinic acid, phthalic acid isomers, etc.), tridentate carboxylates (e.g., citric acid, trimesic acid), azoles (e.g., 1,2,3-triazole), as well as other known organic ligands.
- bidentate carboxylates e.g., oxalic acid, succinic acid, phthalic acid isomers, etc.
- tridentate carboxylates e.g., citric acid, trimesic acid
- azoles e.g., 1,2,3-triazole
- metal organic framework examples include but are not limited to zeolitic imidazole framework (ZIF), HKUST-1.
- Pore sizes may be characterized by a pore size distribution with an average pore size from 2.5 ⁇ to 10.0 ⁇ , and a pore size distribution of at least 0.1 ⁇ .
- the average pore size for the porous material may be in a range with a lower end of 2.5 ⁇ to 4.0 ⁇ and an upper end of 2.6 ⁇ to 10.0 ⁇ . ⁇ .
- the average pore size may be in a range having a lower end of 2.5 ⁇ , 3.0 ⁇ , 3.5 ⁇ , and an upper end of 3.5 ⁇ , 5.0 ⁇ , or 6.0 ⁇ . These range endpoints may be independently combined to form a number of different ranges, and all ranges for each possible combination of range endpoints are hereby disclosed.
- Porosity of the material can be in a range having a lower end of 5 %, 10 %, or 15 %, and an upper end of 85 %, 90 %, or 95 % (percentages by volume). These range endpoints can be independently combined to form a number of different ranges, and all ranges for each possible combination of range endpoints are hereby disclosed.
- microporous materials can be can be synthesized by hydrothermal or solvothermal techniques (e.g., sol-gel,) where crystals are slowly grown from a solution.
- Templating for the microstructure can be provided by a secondary building unit (SBU) and the organic ligands.
- SBU secondary building unit
- Alternate synthesis techniques are also available, such as physical vapor deposition or chemical vapor deposition, in which metal oxide precursor layers are deposited, either as a primary microporous material, or as a precursor to an MOF structure formed by exposure of the precursor layers to sublimed ligand molecules to impart a phase transformation to an MOF crystal lattice.
- the above-described membrane materials may provide a technical effect of promoting separation of contaminants (e.g., nitrogen, oxygen and/or water molecules) from refrigerant gas, which is condensable.
- contaminants e.g., nitrogen, oxygen and/or water molecules
- Other air-permeable materials such as porous or nonporous polymers can be subject to solvent interaction with the matrix material, which can interfere with effective separation.
- the capabilities of the materials described herein can provide a technical effect of promoting the implementation of a various example embodiments of refrigeration systems with purge, as described in more detail with reference to the example embodiments below.
- the membrane material can be self-supporting or it can be supported, for example, as a layer on a porous support or integrated with a matrix support material. Thickness of a support for a supported membrane may range from 50 nm to 1000 nm, more specifically from 100 nm to 750 nm, and even more specifically from 250 nm to 500 nm. In the case of tubular membranes, fiber diameters can range from 100 nm to 2000 nm, and fiber lengths can range from 0.2 m to 2 m.
- the microporous material may be deposited on a support as particles in a powder or dispersed in a liquid carrier using various techniques such as spray coating, dip coating, solution casting, etc.
- the dispersion can contain various additives, such as dispersing aids, rheology modifiers, etc.
- Polymeric additives can be used; however, a polymer binder is not needed, although a polymer binder can be included and in may be included such as with a mixed matrix membrane comprising a microporous inorganic material (e.g., microporous ceramic particles) in an organic (e.g., organic polymer) matrix.
- a polymer binder present in an amount sufficient to form a contiguous polymer phase can provide passageways in the membrane for larger molecules to bypass the molecular sieve particles. Accordingly, in some examples a polymer binder is excluded. In other examples, a polymer binder may be present in an amount below that needed to form a contiguous polymer phase, such as arrangements in which the membrane is in series with other membranes that may be more restrictive.
- Particles of the microporous material may be applied as a powder or dispersed in a liquid carrier (e.g., an organic solvent or aqueous liquid carrier) and coated onto the support followed by removal of the liquid.
- a liquid carrier e.g., an organic solvent or aqueous liquid carrier
- the application of solid particles of microporous material from a liquid composition to the support surface may be assisted by application of a pressure differential across the support. For example a vacuum can be applied from the opposite side of the support as the liquid composition comprising the solid microporous particles to assist in application of the solid particles to the surface of the support.
- a coated layer of microporous material can be dried to remove residual solvent and optionally heated to fuse the microporous particles together into a contiguous layer.
- Various membrane structure configurations can be utilized, including but not limited to flat or planar configurations, tubular configurations, or spiral configurations.
- the membrane may include a protective polymer coating or can utilize backflow or heating to regenerate the membrane, as disclosed in greater detail in US patent application Serial No. 62/584073 , entitled "Low Pressure Refrigeration System with Membrane Purge”.
- the microporous material may be configured as nanoplatelets such as zeolite nanosheets.
- Zeolite nanosheet particles can have thicknesses ranging from 2 to 50 nm, more specifically 2 to 20 nm, and even more specifically from 2 nm to 10 nm.
- the mean diameter of the nanosheets can range from 50 nm to 5000 nm, more specifically from 100 nm to 2500 nm, and even more specifically from 100 nm to 1000 nm.
- Mean diameter of an irregularly-shaped tabular particle can be determined by calculating the diameter of a circular-shaped tabular particle having the same surface area in the x-y direction (i.e., along the tabular planar surface) as the irregularly-shaped particle.
- Zeolite such as zeolite nanosheets can be formed from any of various zeolite structures, including but not limited to framework type MFI, MWW, FER, LTA, FAU, and mixtures of the preceding with each other or with other zeolite structures.
- the zeolite such as zeolite nanosheets can comprise zeolite structures selected from MFI, MWW, FER, LTA framework type.
- Zeolite nanosheets can be prepared using known techniques such as exfoliation of zeolite crystal structure precursors.
- MFI and MWW zeolite nanosheets can be prepared by sonicating the layered precursors (multilamellar silicalite-1 and ITQ-1, respectively) in solvent.
- the zeolite layers Prior to sonication, can optionally be swollen, for example with a combination of base and surfactant, and/or melt-blending with polystyrene.
- the zeolite layered precursors are typically prepared using conventional techniques for preparation of microporous materials such as sol-gel methods.
- the membrane purge shown in FIG. 1 can be used with various types of refrigeration systems.
- One example system is a vapor compression cycle refrigeration system, an example of which is shown in FIG. 2 .
- a heat transfer fluid circulation loop is shown in block diagram form in FIG. 2 .
- a compressor 10 pressurizes heat transfer fluid in its gaseous state, which both heats the fluid and provides pressure to circulate it throughout the system.
- the heat transfer fluid, or refrigerant may comprise an organic compound.
- the refrigerant may comprise a hydrocarbon or substituted hydrocarbon.
- the refrigerant may comprise a halogen-substituted hydrocarbon.
- the refrigerant may comprise a fluoro-substituted or chloro-fluoro-substituted hydrocarbon.
- the hot pressurized gaseous heat transfer fluid exiting from the compressor 10 flows through conduit 15 to a heat rejection heat exchanger such as condenser 20, which functions as a heat exchanger to transfer heat from the heat transfer fluid to the surrounding environment, resulting in condensation of the hot gaseous heat transfer fluid to a pressurized moderate temperature liquid.
- the liquid heat transfer fluid exiting from the condenser 20 flows through conduit 25 to expansion valve 30, where the pressure is reduced.
- the reduced pressure liquid heat transfer fluid exiting the expansion valve 30 flows through conduit 35 to a heat absorption heat exchanger such as evaporator 40, which functions as a heat exchanger to absorb heat from the surrounding environment and boil the heat transfer fluid.
- Gaseous heat transfer fluid exiting the evaporator 40 flows through conduit 45 to the compressor 10, thus completing the heat transfer fluid loop.
- the heat transfer system has the effect of transferring heat from the environment surrounding the evaporator 40 to the environment surrounding the condenser 20.
- the thermodynamic properties of the heat transfer fluid must allow it to reach a high enough temperature when compressed so that it is greater than the environment surrounding the condenser 20, allowing heat to be transferred to the surrounding environment.
- the thermodynamic properties of the heat transfer fluid must also have a boiling point at its post-expansion pressure that allows the temperature surrounding the evaporator 40 to provide heat to vaporize the liquid heat transfer fluid.
- a purge collector 66 receives purge gas including refrigerant gas and contaminants (e.g., nitrogen, oxygen) from a purge connection 52 connected to the condenser 20.
- the purge gas is directed from the purge collector 66 to a first side of a membrane 56 in a membrane separator 54.
- the membrane separator 54 and purge collector 66 may be integrated into a single unit by disposing the membrane 56 at the outlet of the purge collector 66.
- a prime mover such as a vacuum pump 58 connected to the membrane separator 54 provides a driving force to pass the contaminant gas molecules through the membrane 56 and exit the system from a second side of the membrane 56 through an outlet.
- a controller 50 receives system data (e.g., pressure, temperature, mass flow rates) and system or operator control (e.g., on/of, receipt of cooling demand signal), and utilizes electronic control components (e.g., a microprocessor) to control system components such as various pumps, valves, switches.
- the connection of the purge connection 52 to the condenser may be made at a high point of the condenser structure.
- the purge collector 66 may provide a technical effect of promoting higher concentrations of contaminants at the membrane separator 54, which can promote more effective mass transfer and separation. This effect can occur through a stratification of gas in the purge collector 66 in which lighter contaminants concentrates toward the top of the purge collector 66 and heavier refrigerant gas concentrates toward the bottom of the purge collector 66.
- the the purge collector 66 may be any kind of vessel or chamber with a volume or cross-sectional open space to provide for collection of purge gas and for a low gas velocity during operation of the purge system vacuum pump 58 to promote stratification.
- Stratification can also occur at any time when the purge system is not operating (including during operation of the refrigeration system fluid circulation loop), as the purge collector 66 remains in fluid communication with the purge connection 52 with essentially stagnant gas in the purge collector 66.
- Other arrangements can also be employed to promote higher concentrations of contaminants at the membrane separator 54, as discussed in more detail below.
- Refrigerant from the first side of membrane 56 may be returned to the refrigerant fluid circulation loop.
- a connection 67 returns retentate gas from the first side of membrane 56 to the refrigerant fluid circulation loop at the evaporator 40, through a control device such as expansion valve 68 utilized to accommodate the pressure differential between the first side of the membrane 56 (which is close to the pressure at the condenser 20) and pressure at the evaporator 40.
- the control device can control either or both flow through or pressure drop across the control device, and expansion valve 68 is shown as an integrated control device unit that performs both functions for ease of illustration, but could be separate components such as a control valve and an expansion orifice.
- Utilization of a bypass refrigerant return may provide a technical effect of promoting greater concentrations of contaminants at the first side of membrane 56 by removing gas at the membrane 56 that is concentrated with refrigerant after removal of contaminant gas molecules through the membrane 56, so that refrigerant-concentrated gas can be displaced with gas from the purge collector 66 that has a higher concentration of contaminants.
- the bypass 67 can also include a control or shut-off valve, which can be integrated with an expansion device (i.e., an expansion valve), as described in more detail in US patent application Serial No. 62/584,012 .
- the bypass conduit 67 can return refrigerant-laden gas to a colder side of the condenser 20 or inlet of the compressor 10, in which case an expansion device may not be needed due to lower pressure differential compared to that of a bypass return to the evaporator 40.
- the connection 67 can utilize a control device such as a control or shut-off valve 69 that does not provide gas expansion.
- gas stratification in the purge collector 66 may provide a technical effect of promoting higher concentrations of contaminants at the first side of the membrane 56, which in turn can promote more effective mass transfer to the membrane and more effective separation.
- FIGS. 5 and 6 show schematic depictions of arrangements that can promote stratification and/or delivery of higher concentrations of contaminants to the membrane 56.
- a cooling element such as a heat exchange coil loop 70 in fluid communication with cold refrigerant from the evaporator can be disposed in the purge collector 66 to promote stratification through thermally-induced densification of refrigerant gas and/or through condensation of refrigerant gas.
- a centrifugal separator 72 can promote stratification in the purge collector 66 by directing relatively dense refrigerant gas radially outward (from where it can be directed downward or back to the refrigerant fluid flow loop) while relatively less dense contaminant gases can flow upward through the purge collector 66 and on to the membrane separator 54.
- Centrifugal separators can utilize a vortex-inducing blade or other assembly at an upstream of the separator and components (e.g., walls and channels) disposed radially outward for collecting separated gas of higher density.
- FIG. 7 shows a permeate recycle 74 that directs a portion of the contaminants on the second side of the membrane 56 back to the first side of the membrane.
- Recycle 74 can include a conduit with a pump (e.g., a Venturi-style pump using pressurized fluid from the refrigerant fluid flow loop or a small mechanical pump).
- FIG. 8 An example of a cascaded configuration is schematically depicted in FIG. 8 .
- membrane separation units 54a and 54b (with membranes 56a and 56b) are disposed in a cascaded configuration in which permeate from the separation unit 54a is fed to the first side of the second separation unit 54b.
- Retentate from the first side of the membranes 56a and 56b is routed through connections 67a and 67b to the refrigerant fluid circulation loop at the evaporator 40, with expansion devices 68a and 68b utilized to accommodate the pressure differential between the first side of membranes 56a and 56b (which is close to the pressure at the condenser 20) and pressure at the evaporator 40.
- expansion devices 68a and 68b utilized to accommodate the pressure differential between the first side of membranes 56a and 56b (which is close to the pressure at the condenser 20) and pressure at the evaporator 40.
- Prime mover can involve the prime mover.
- the above-discussed examples utilize a vacuum pump in communication with the permeate side of the membrane, but other prime movers can be utilized.
- mechanical vacuum pumps such as a vane pump or reciprocating piston pump
- Venturi-style pumps can be used in which a flowing fluid (e.g., refrigerant flowing through the refrigerant fluid flow loop is routed through a Venturi device in fluid communication with the permeate side of the membrane to draw a vacuum on the permeate side of the membrane.
- a prime mover is shown in FIG.
- a heat source 76 can be activated to heat the gas in the purge collector 66 in conjunction with isolating the purge collector from the condenser, such as with a shut-off valve or check-valve to cause thermal expansion and thereby provide motive force to drive gas to and through the membrane 56.
- the heat source 76 (or a different heat source) can also be used to control the membrane temperature during operation to achieve target membrane performance characteristics, or to heat the membrane for membrane regeneration.
- the system includes a controller such as controller 50 for controlling the operation of the heat transfer refrigerant flow loop and the purge system.
- a refrigeration or chiller system controller can operate the refrigerant heat transfer flow loop in response to a cooling demand signal, which can be generated externally to the system by a master controller or can be entered by a human operator. Some systems can be configured to operate the flow loop continuously for extended periods.
- the controller is configured to also operate the control device in the retentate return conduit, or the prime mover, or both the control device and the prime mover, in response to a purge signal.
- the purge signal can be generated from various criteria.
- the purge signal can be in response to elapse of a predetermined amount of time (e.g., simple passage of time, or tracked operating hours) tracked by the controller circuitry.
- the purge signal may be in response to human operator input.
- the purge signal may be in response to measured parameters of the refrigerant fluid flow loop, such as a pressure sensor.
Description
- This disclosure relates generally to chiller systems used in air conditioning systems, and more particularly to a purge system for removing contaminants from a refrigeration system.
- Chiller systems such as those utilizing centrifugal compressors may include sections that operate below atmospheric pressure. As a result, leaks in the chiller system may draw air into the system, contaminating the refrigerant. This contamination degrades the performance of the chiller system. To address this problem, existing low pressure chillers include a purge unit to remove contamination. Existing purge units use a vapor compression cycle to separate contaminant gas from the refrigerant. Existing purge units are complicated and lose refrigerant in the process of removing contamination. Document
US 5 044 166 A discloses a refrigeration system according to the preamble of claim 1 - The present invention provides a refrigeration system as in claim 1 and a method for operating a refrigeration system as in claim 12. Disclosed is a refrigeration system including a heat transfer fluid circulation loop configured to allow a refrigerant to circulate therethrough. A purge gas outlet is in operable communication with the heat transfer fluid circulation loop. The system also includes at least one gas permeable membrane having a first side in operable communication with the purge gas outlet and a second side. The membrane includes a porous inorganic material with pores of a size to allow passage of contaminants through the membrane and restrict passage of the refrigerant through the membrane. The system also includes a permeate outlet in operable communication with a second side of the membrane.
- In some embodiments, the system further includes a prime mover operably coupled to the permeate outlet, and the prime mover is configured to move gas from the second side of the membrane to an exhaust port leading outside the fluid circulation loop.
- In any one or combination of the foregoing embodiments, the heat transfer fluid circulation loop includes a compressor, a heat rejection heat exchanger, an expansion device, and a heat absorption heat exchanger, connected together in order by conduit, and the purge gas outlet is in operable communication with at least one of the heat rejection heat exchanger, the heat absorption heat exchanger and the membrane.
- In any one or combination of the foregoing embodiments, the system further includes a retentate return conduit operably coupling the first side of the membrane to the fluid circulation loop. In some embodiments, the prime mover is a vacuum pump
- In any one or combination of the foregoing embodiments, the system further includes a purge gas collector operably coupled to the purge outlet and the membrane.
- In any one or combination of the foregoing embodiments, the purge gas collector includes purge gas therein comprising refrigerant gas and contaminants, said purge gas in a stratified configuration with a higher concentration of refrigerant toward the purge outlet and a higher concentration of contaminants toward the membrane.
- In any one or combination of the foregoing embodiments, the system further includes a chiller coil disposed in the purge gas collector, the coil in operable communication with the fluid circulation loop.
- In any one or combination of the foregoing embodiments, the system further includes a heat source, said heat source being in controllable thermal communication with at least one of the membrane and the purge gas collector.
- In any one or combination of the foregoing embodiments, the system further includes a heat source in controllable thermal communication with either or both of the membrane or a purge gas collector between the purge outlet and the membrane.
- In any one or combination of the foregoing embodiments, the membrane includes a ceramic.
- In any one or combination of the foregoing embodiments, the at least one gas permeable membrane includes a plurality of gas permeable membranes; wherein the plurality of gas permeable membranes are arranged in serial or parallel communication.
- In any one or combination, of the foregoing embodiments, the system further includes a second prime mover conduit to move permeate from the second side of the membrane to the first side of the membrane.
- In any one or combination of the foregoing embodiments, the system further includes a filter or a vortex separator between the purge outlet and the membrane.
- In any one or combination of the foregoing embodiments, the system further includes a controller configured to operate fluid circulation loop in response to a cooling demand signal and to operate the prime mover in response to a determination of contaminants in the fluid circulation loop.
- Also disclosed is a method of operating a refrigeration system, including circulating a refrigerant through a vapor compression heat transfer fluid circulation loop in response to a cooling demand signal. The fluid circulation loop includes a heat rejection side of a first heat exchanger, an expansion device, and the heat absorption side of a second heat exchanger, connected together in order by conduit under conditions in which the refrigerant is at a pressure less than atmospheric pressure in at least a portion of the fluid circulation loop. Purge gas including contaminants is collected from a purge outlet in the fluid circulation loop and transferred across a permeable membrane with a prime mover. The membrane includes a porous inorganic material with pores of a size to allow passage of the contaminants through the membrane and restrict passage of the refrigerant through the membrane.
- In some embodiments, the method further includes collecting the purge gas in a purge gas collector between the purge outlet and the membrane.
- In any one or combination of the foregoing embodiments, the method includes stratifying purge gas in the purge gas collector with a higher concentration of refrigerant toward the purge outlet and a higher concentration of contaminants toward the membrane.
- In any one or combination of the foregoing embodiments, the method further includes returning refrigerant from the first side of the membrane to the fluid circulation loop.
- Preferred embodiments of the invention will now be described by way of example only and with reference to the accompanying drawings, as listed below. The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:
-
FIG. 1 is a schematic depiction of a membrane purge system for a refrigeration system; -
FIG. 2 is a schematic depiction of a refrigeration system including a vapor compression heat transfer refrigerant fluid circulation loop; -
FIG. 3 is schematic depiction of a membrane purge system with purge collector and relevant components of a vapor compression heat transfer refrigerant fluid circulation loop; -
FIG. 4 is schematic depiction of a purge system and relevant components of a vapor compression heat transfer refrigerant fluid circulation loop, with membrane unit retentate directed to the system evaporator; -
FIG. 5 is schematic depiction of another example of a purge system and relevant components of a vapor compression heat transfer refrigerant fluid circulation loop, with a cooling element in a purge collector; -
FIG. 6 is schematic depiction of another example of a purge system and relevant components of a vapor compression heat transfer refrigerant fluid circulation loop, with a centrifugal separator; -
FIG. 7 is schematic depiction of another example of a purge system and relevant components of a vapor compression heat transfer refrigerant fluid circulation loop, with a permeate recycle; -
FIG. 8 is a schematic depiction of another example of a purge system and relevant components of a vapor compression heat transfer refrigerant fluid circulation loop, with membrane units in a cascade configuration; and -
FIG. 9 is a schematic depiction of another example of a purge system and relevant components of a vapor compression heat transfer refrigerant fluid circulation loop, with a thermal prime mover. - A detailed description of one or more embodiments of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figures.
- With reference now to
FIG. 1 , there is shown an example of a purge system that can be connected to a heat transfer fluid circulation loop such as the one shown inFIG. 2 . As shown inFIG. 1 , the purge system receives gas comprising refrigerant gas and contaminants (e.g., nitrogen, oxygen, or water) from a refrigerant-containing refrigeration system such as shown in FIG. 12 through apurge connection 52 to amembrane separator 54 on a first side of amembrane 56. The contaminants may comprise a non-condensable gas such as components of atmospheric air (e.g., nitrogen, oxygen). A prime mover such as avacuum pump 58 connected to themembrane separator 54 throughconnection 60 provides a driving force to pass the contaminant molecules through themembrane 56 and exit the system from a second side of themembrane 56 through anoutlet 58. The prime mover may be in the fluid loop, e.g., a refrigerant pump or compressor. Refrigerant gas tends to remain on the first side of themembrane 56 and can return to the fluid circulation loop throughconnection 64. Acontroller 50, the operation of which is described in more detail below, is in operable communication with the refrigeration system components. - The
membrane 56 includes a porous inorganic material. Examples of porous inorganic materials can include ceramics such as metal oxides or metal silicates, more specifically aluminosilicates (e.g., Chabazite Framework (CHA) zeolite, Linde type A (LTA) zeolite, porous carbon, porous glass, clays (e.g., Montmorillonite, Halloysite). Porous inorganic materials can also include porous metals such as platinum and nickel. Hybrid inorganic-organic materials such as a metal organic framework (MOF) can also be used. Other materials can be present in the membrane such as a carrier in which a microporous material can be dispersed, which can be included for structural or process considerations. - Metal organic framework materials are well-known in the art, and comprise metal ions or clusters of metal ions coordinated to organic ligands to form one-, two- or three-dimensional structures. A metal-organic framework can be characterized as a coordination network with organic ligands containing voids. The coordination network can be characterized as a coordination compound extending, through repeating coordination entities, in one dimension, but with cross-links between two or more individual chains, loops, or spiro-links, or a coordination compound extending through repeating coordination entities in two or three dimensions. Coordination compounds can include coordination polymers with repeating coordination entities extending in one, two, or three dimensions. Examples of organic ligands include but are not limited to bidentate carboxylates (e.g., oxalic acid, succinic acid, phthalic acid isomers, etc.), tridentate carboxylates (e.g., citric acid, trimesic acid), azoles (e.g., 1,2,3-triazole), as well as other known organic ligands. A wide variety of metals can be included in a metal organic framework. Examples of specific metal organic framework materials include but are not limited to zeolitic imidazole framework (ZIF), HKUST-1.
- Pore sizes may be characterized by a pore size distribution with an average pore size from 2.5 Å to 10.0 Å, and a pore size distribution of at least 0.1 Å. The average pore size for the porous material may be in a range with a lower end of 2.5 Å to 4.0 Å and an upper end of 2.6 Å to 10.0 Å. Å. The average pore size may be in a range having a lower end of 2.5 Å, 3.0 Å, 3.5 Å, and an upper end of 3.5 Å, 5.0 Å, or 6.0 Å. These range endpoints may be independently combined to form a number of different ranges, and all ranges for each possible combination of range endpoints are hereby disclosed. Porosity of the material can be in a range having a lower end of 5 %, 10 %, or 15 %, and an upper end of 85 %, 90 %, or 95 % (percentages by volume). These range endpoints can be independently combined to form a number of different ranges, and all ranges for each possible combination of range endpoints are hereby disclosed.
- The above microporous materials can be can be synthesized by hydrothermal or solvothermal techniques (e.g., sol-gel,) where crystals are slowly grown from a solution. Templating for the microstructure can be provided by a secondary building unit (SBU) and the organic ligands. Alternate synthesis techniques are also available, such as physical vapor deposition or chemical vapor deposition, in which metal oxide precursor layers are deposited, either as a primary microporous material, or as a precursor to an MOF structure formed by exposure of the precursor layers to sublimed ligand molecules to impart a phase transformation to an MOF crystal lattice.
- The above-described membrane materials may provide a technical effect of promoting separation of contaminants (e.g., nitrogen, oxygen and/or water molecules) from refrigerant gas, which is condensable. Other air-permeable materials, such as porous or nonporous polymers can be subject to solvent interaction with the matrix material, which can interfere with effective separation. In some embodiments, the capabilities of the materials described herein can provide a technical effect of promoting the implementation of a various example embodiments of refrigeration systems with purge, as described in more detail with reference to the example embodiments below.
- The membrane material can be self-supporting or it can be supported, for example, as a layer on a porous support or integrated with a matrix support material. Thickness of a support for a supported membrane may range from 50 nm to 1000 nm, more specifically from 100 nm to 750 nm, and even more specifically from 250 nm to 500 nm. In the case of tubular membranes, fiber diameters can range from 100 nm to 2000 nm, and fiber lengths can range from 0.2 m to 2 m.
- The microporous material may be deposited on a support as particles in a powder or dispersed in a liquid carrier using various techniques such as spray coating, dip coating, solution casting, etc. The dispersion can contain various additives, such as dispersing aids, rheology modifiers, etc. Polymeric additives can be used; however, a polymer binder is not needed, although a polymer binder can be included and in may be included such as with a mixed matrix membrane comprising a microporous inorganic material (e.g., microporous ceramic particles) in an organic (e.g., organic polymer) matrix. However, a polymer binder present in an amount sufficient to form a contiguous polymer phase can provide passageways in the membrane for larger molecules to bypass the molecular sieve particles. Accordingly, in some examples a polymer binder is excluded. In other examples, a polymer binder may be present in an amount below that needed to form a contiguous polymer phase, such as arrangements in which the membrane is in series with other membranes that may be more restrictive. Particles of the microporous material (e.g., particles with sizes of 0.01 µm to 10 µm, or in some embodiments from 0.5 µm to 10 µm) may be applied as a powder or dispersed in a liquid carrier (e.g., an organic solvent or aqueous liquid carrier) and coated onto the support followed by removal of the liquid. The application of solid particles of microporous material from a liquid composition to the support surface may be assisted by application of a pressure differential across the support. For example a vacuum can be applied from the opposite side of the support as the liquid composition comprising the solid microporous particles to assist in application of the solid particles to the surface of the support. A coated layer of microporous material can be dried to remove residual solvent and optionally heated to fuse the microporous particles together into a contiguous layer. Various membrane structure configurations can be utilized, including but not limited to flat or planar configurations, tubular configurations, or spiral configurations. The membrane may include a protective polymer coating or can utilize backflow or heating to regenerate the membrane, as disclosed in greater detail in
US patent application Serial No. 62/584073 - The microporous material may be configured as nanoplatelets such as zeolite nanosheets. Zeolite nanosheet particles can have thicknesses ranging from 2 to 50 nm, more specifically 2 to 20 nm, and even more specifically from 2 nm to 10 nm. The mean diameter of the nanosheets can range from 50 nm to 5000 nm, more specifically from 100 nm to 2500 nm, and even more specifically from 100 nm to 1000 nm. Mean diameter of an irregularly-shaped tabular particle can be determined by calculating the diameter of a circular-shaped tabular particle having the same surface area in the x-y direction (i.e., along the tabular planar surface) as the irregularly-shaped particle. Zeolite such as zeolite nanosheets can be formed from any of various zeolite structures, including but not limited to framework type MFI, MWW, FER, LTA, FAU, and mixtures of the preceding with each other or with other zeolite structures. In a more specific group of examples, the zeolite such as zeolite nanosheets can comprise zeolite structures selected from MFI, MWW, FER, LTA framework type. Zeolite nanosheets can be prepared using known techniques such as exfoliation of zeolite crystal structure precursors. For example, MFI and MWW zeolite nanosheets can be prepared by sonicating the layered precursors (multilamellar silicalite-1 and ITQ-1, respectively) in solvent. Prior to sonication, the zeolite layers can optionally be swollen, for example with a combination of base and surfactant, and/or melt-blending with polystyrene. The zeolite layered precursors are typically prepared using conventional techniques for preparation of microporous materials such as sol-gel methods.
- The membrane purge shown in
FIG. 1 can be used with various types of refrigeration systems. One example system is a vapor compression cycle refrigeration system, an example of which is shown inFIG. 2 . As shown inFIG. 2 , a heat transfer fluid circulation loop is shown in block diagram form inFIG. 2 . As shown inFIG. 2 , acompressor 10 pressurizes heat transfer fluid in its gaseous state, which both heats the fluid and provides pressure to circulate it throughout the system. The heat transfer fluid, or refrigerant, may comprise an organic compound. The refrigerant may comprise a hydrocarbon or substituted hydrocarbon. The refrigerant may comprise a halogen-substituted hydrocarbon. The refrigerant may comprise a fluoro-substituted or chloro-fluoro-substituted hydrocarbon. The hot pressurized gaseous heat transfer fluid exiting from thecompressor 10 flows throughconduit 15 to a heat rejection heat exchanger such ascondenser 20, which functions as a heat exchanger to transfer heat from the heat transfer fluid to the surrounding environment, resulting in condensation of the hot gaseous heat transfer fluid to a pressurized moderate temperature liquid. The liquid heat transfer fluid exiting from thecondenser 20 flows throughconduit 25 toexpansion valve 30, where the pressure is reduced. The reduced pressure liquid heat transfer fluid exiting theexpansion valve 30 flows throughconduit 35 to a heat absorption heat exchanger such asevaporator 40, which functions as a heat exchanger to absorb heat from the surrounding environment and boil the heat transfer fluid. Gaseous heat transfer fluid exiting theevaporator 40 flows throughconduit 45 to thecompressor 10, thus completing the heat transfer fluid loop. The heat transfer system has the effect of transferring heat from the environment surrounding theevaporator 40 to the environment surrounding thecondenser 20. The thermodynamic properties of the heat transfer fluid must allow it to reach a high enough temperature when compressed so that it is greater than the environment surrounding thecondenser 20, allowing heat to be transferred to the surrounding environment. The thermodynamic properties of the heat transfer fluid must also have a boiling point at its post-expansion pressure that allows the temperature surrounding theevaporator 40 to provide heat to vaporize the liquid heat transfer fluid. - With reference now to
FIG. 3 , there is shown a purge system connected to a vapor compression heat transfer fluid circulation loop such asFIG. 2 (not all components ofFIG. 2 shown). As shown inFIG. 3 , apurge collector 66 receives purge gas including refrigerant gas and contaminants (e.g., nitrogen, oxygen) from apurge connection 52 connected to thecondenser 20. The purge gas is directed from thepurge collector 66 to a first side of amembrane 56 in amembrane separator 54. Themembrane separator 54 andpurge collector 66 may be integrated into a single unit by disposing themembrane 56 at the outlet of thepurge collector 66. A prime mover such as avacuum pump 58 connected to themembrane separator 54 provides a driving force to pass the contaminant gas molecules through themembrane 56 and exit the system from a second side of themembrane 56 through an outlet. Acontroller 50 receives system data (e.g., pressure, temperature, mass flow rates) and system or operator control (e.g., on/of, receipt of cooling demand signal), and utilizes electronic control components (e.g., a microprocessor) to control system components such as various pumps, valves, switches. - The connection of the
purge connection 52 to the condenser may be made at a high point of the condenser structure. Thepurge collector 66 may provide a technical effect of promoting higher concentrations of contaminants at themembrane separator 54, which can promote more effective mass transfer and separation. This effect can occur through a stratification of gas in thepurge collector 66 in which lighter contaminants concentrates toward the top of thepurge collector 66 and heavier refrigerant gas concentrates toward the bottom of thepurge collector 66. The thepurge collector 66 may be any kind of vessel or chamber with a volume or cross-sectional open space to provide for collection of purge gas and for a low gas velocity during operation of the purgesystem vacuum pump 58 to promote stratification. Stratification can also occur at any time when the purge system is not operating (including during operation of the refrigeration system fluid circulation loop), as thepurge collector 66 remains in fluid communication with thepurge connection 52 with essentially stagnant gas in thepurge collector 66. Other arrangements can also be employed to promote higher concentrations of contaminants at themembrane separator 54, as discussed in more detail below. - Refrigerant from the first side of
membrane 56 may be returned to the refrigerant fluid circulation loop. As shown inFIG. 4 , aconnection 67 returns retentate gas from the first side ofmembrane 56 to the refrigerant fluid circulation loop at theevaporator 40, through a control device such asexpansion valve 68 utilized to accommodate the pressure differential between the first side of the membrane 56 (which is close to the pressure at the condenser 20) and pressure at theevaporator 40. It should be noted that the control device can control either or both flow through or pressure drop across the control device, andexpansion valve 68 is shown as an integrated control device unit that performs both functions for ease of illustration, but could be separate components such as a control valve and an expansion orifice. Utilization of a bypass refrigerant return may provide a technical effect of promoting greater concentrations of contaminants at the first side ofmembrane 56 by removing gas at themembrane 56 that is concentrated with refrigerant after removal of contaminant gas molecules through themembrane 56, so that refrigerant-concentrated gas can be displaced with gas from thepurge collector 66 that has a higher concentration of contaminants. Thebypass 67 can also include a control or shut-off valve, which can be integrated with an expansion device (i.e., an expansion valve), as described in more detail inUS patent application Serial No. 62/584,012 bypass conduit 67 can return refrigerant-laden gas to a colder side of thecondenser 20 or inlet of thecompressor 10, in which case an expansion device may not be needed due to lower pressure differential compared to that of a bypass return to theevaporator 40. In such as case, theconnection 67 can utilize a control device such as a control or shut-off valve 69 that does not provide gas expansion. - As discussed above, gas stratification in the
purge collector 66 may provide a technical effect of promoting higher concentrations of contaminants at the first side of themembrane 56, which in turn can promote more effective mass transfer to the membrane and more effective separation.FIGS. 5 and6 show schematic depictions of arrangements that can promote stratification and/or delivery of higher concentrations of contaminants to themembrane 56. As shown inFIG. 5 , a cooling element such as a heatexchange coil loop 70 in fluid communication with cold refrigerant from the evaporator can be disposed in thepurge collector 66 to promote stratification through thermally-induced densification of refrigerant gas and/or through condensation of refrigerant gas. As shown inFIG. 6 , acentrifugal separator 72 can promote stratification in thepurge collector 66 by directing relatively dense refrigerant gas radially outward (from where it can be directed downward or back to the refrigerant fluid flow loop) while relatively less dense contaminant gases can flow upward through thepurge collector 66 and on to themembrane separator 54. Centrifugal separators can utilize a vortex-inducing blade or other assembly at an upstream of the separator and components (e.g., walls and channels) disposed radially outward for collecting separated gas of higher density. - In another example that can promote a higher relative concentration of contaminants at the first side of the
membrane 56,FIG. 7 shows apermeate recycle 74 that directs a portion of the contaminants on the second side of themembrane 56 back to the first side of the membrane.Recycle 74 can include a conduit with a pump (e.g., a Venturi-style pump using pressurized fluid from the refrigerant fluid flow loop or a small mechanical pump). - The above discussion relates to examples of specific embodiments, and other variations and modifications may be made. For example, a single membrane is depicted for ease of illustration in the above-discussed Figures. However, multiple membranes (or membrane separation units) can be utilized, either in cascaded or parallel configurations. An example of a cascaded configuration is schematically depicted in
FIG. 8 . As shown inFIG. 8 ,membrane separation units membranes separation unit 54a is fed to the first side of thesecond separation unit 54b. Retentate from the first side of themembranes connections evaporator 40, withexpansion devices membranes evaporator 40. Other variations for protection of the membrane through a polymer layer or regenerative back-flush or heating cycles are disclosed inUS patent application Serial No. 62/584,073 - Other system variations can involve the prime mover. The above-discussed examples utilize a vacuum pump in communication with the permeate side of the membrane, but other prime movers can be utilized. As an alternative to mechanical vacuum pumps such as a vane pump or reciprocating piston pump, Venturi-style pumps can be used in which a flowing fluid (e.g., refrigerant flowing through the refrigerant fluid flow loop is routed through a Venturi device in fluid communication with the permeate side of the membrane to draw a vacuum on the permeate side of the membrane. Another example of a prime mover is shown in
FIG. 9 , in which aheat source 76 can be activated to heat the gas in thepurge collector 66 in conjunction with isolating the purge collector from the condenser, such as with a shut-off valve or check-valve to cause thermal expansion and thereby provide motive force to drive gas to and through themembrane 56. The heat source 76 (or a different heat source) can also be used to control the membrane temperature during operation to achieve target membrane performance characteristics, or to heat the membrane for membrane regeneration. - As mentioned above, the system includes a controller such as
controller 50 for controlling the operation of the heat transfer refrigerant flow loop and the purge system. A refrigeration or chiller system controller can operate the refrigerant heat transfer flow loop in response to a cooling demand signal, which can be generated externally to the system by a master controller or can be entered by a human operator. Some systems can be configured to operate the flow loop continuously for extended periods. The controller is configured to also operate the control device in the retentate return conduit, or the prime mover, or both the control device and the prime mover, in response to a purge signal. The purge signal can be generated from various criteria. In some embodiments, the purge signal can be in response to elapse of a predetermined amount of time (e.g., simple passage of time, or tracked operating hours) tracked by the controller circuitry. The purge signal may be in response to human operator input. The purge signal may be in response to measured parameters of the refrigerant fluid flow loop, such as a pressure sensor. - The term "about", if used, is intended to include the degree of error associated with measurement of the particular quantity based upon the equipment available at the time of filing the application. For example, "about" may include a range of ± 8% or 5%, or 2% of a given value and thus any references to "about" should be taken to include those possible ranges.
- The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, element components, and/or groups thereof.
- While the present disclosure has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the claims. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present disclosure. Therefore, it is intended that the present invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this present disclosure, but that the present invention will include all embodiments falling within the scope of the claims.
Claims (12)
- A refrigeration system comprising
a heat transfer fluid circulation loop configured to allow a refrigerant to circulate therethrough;
a purge gas outlet in operable communication with the heat transfer fluid circulation loop;
at least one gas permeable membrane (56) having a first side in operable communication with the purge gas outlet and a second side, said membrane comprising a porous inorganic material with pores of a size to allow passage of contaminants through the membrane and restrict passage of the refrigerant through the membrane;
a permeate outlet in operable communication with the second side of the membrane; and
a prime mover (58) configured to provide a driving force to pass the contaminants through the membrane to the permeate outlet, characterized in that:
the system includes a heat source (76) in controllable thermal communication with the membrane or with a purge gas collector (66) operably coupled to the purge gas outlet and the membrane, and/or
the system includes a controller (50) configured to operate fluid circulation loop in response to a cooling demand signal and to operate the prime mover in response to a determination of contaminants in the fluid circulation loop, and/or
the system includes a second prime mover and conduit configured to move permeate from the second side of the membrane to the first side of the membrane. - The refrigeration system of claim 1, comprising a retentate return conduit operably coupling the first side of the membrane to the fluid circulation loop.
- The refrigeration system of claim 1 or 2, wherein the prime mover is operably coupled to the permeate outlet, and is configured to move gas from the second side of the membrane to an exhaust port leading outside the fluid circulation loop.
- The refrigeration system of any preceding claim, wherein the heat transfer fluid circulation loop comprises a compressor, a heat rejection heat exchanger, an expansion device, and a heat absorption heat exchanger, connected together in order by conduit; and
wherein the purge gas outlet is in operable communication with at least one of the heat rejection heat exchanger, the heat absorption heat exchanger and the membrane. - The refrigeration system of any preceding claim, wherein the prime mover comprises a vacuum pump.
- The refrigeration system of any preceding claim, comprising a purge gas collector operably coupled to the purge outlet and the membrane.
- The refrigeration system of claim 6, wherein the purge gas collector comprises purge gas therein, the purge gas comprising refrigerant gas and contaminants, said purge gas being in a stratified configuration with a higher concentration of refrigerant toward the purge outlet and a higher concentration of contaminants toward the membrane.
- The refrigeration system of claims 6 or 7, comprising a chiller coil disposed in the purge gas collector, the coil in operable communication with the fluid circulation loop.
- The refrigeration system of any preceding claim, wherein the membrane comprises a ceramic.
- The refrigeration system of any preceding claim, wherein the at least one gas permeable membrane comprises a plurality of gas permeable membranes; wherein the plurality of gas permeable membranes are arranged in serial or parallel communication.
- The refrigeration system of any preceding claim, further comprising a filter or a vortex separator between the purge outlet and the membrane.
- A method of operating refrigeration system of any of the preceding claims, the method comprising:circulating a refrigerant through the fluid circulation loop in response to a cooling demand signal,;collecting purge gas comprising contaminants from the purge gas outlet; andoperating the prime mover to transfer contaminants across the permeable membrane.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/808,837 US10584906B2 (en) | 2013-08-09 | 2017-11-09 | Refrigeration purge system |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3483530A1 EP3483530A1 (en) | 2019-05-15 |
EP3483530B1 true EP3483530B1 (en) | 2020-12-30 |
Family
ID=64267699
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18205247.2A Active EP3483530B1 (en) | 2017-11-09 | 2018-11-08 | Refrigeration purge system |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3483530B1 (en) |
CN (1) | CN110595257B (en) |
ES (1) | ES2845218T3 (en) |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4417451A (en) * | 1980-05-07 | 1983-11-29 | Hilliard-Lyons Patent Management, Inc. | Vapor compression refrigerant system monitor and gas removal apparatus |
US5044166A (en) * | 1990-03-05 | 1991-09-03 | Membrane Technology & Research, Inc. | Refrigeration process with purge and recovery of refrigerant |
US5062273A (en) * | 1990-07-12 | 1991-11-05 | E. I. Du Pont De Nemours And Company | Method and apparatus for removal of gas from refrigeration system |
JP4007307B2 (en) * | 2003-10-22 | 2007-11-14 | ダイキン工業株式会社 | Refrigeration equipment construction method |
EP3030850B1 (en) * | 2013-08-09 | 2020-12-23 | Carrier Corporation | Purge system for chiller system |
CN103438491B (en) * | 2013-08-28 | 2016-04-27 | 南通大学 | With hot water supply and the heating system of the employing heat pump of hot water self-circulation system |
-
2018
- 2018-11-08 ES ES18205247T patent/ES2845218T3/en active Active
- 2018-11-08 EP EP18205247.2A patent/EP3483530B1/en active Active
- 2018-11-08 CN CN201811323689.6A patent/CN110595257B/en active Active
Non-Patent Citations (1)
Title |
---|
None * |
Also Published As
Publication number | Publication date |
---|---|
ES2845218T3 (en) | 2021-07-26 |
CN110595257A (en) | 2019-12-20 |
EP3483530A1 (en) | 2019-05-15 |
CN110595257B (en) | 2022-06-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10584906B2 (en) | Refrigeration purge system | |
US11911724B2 (en) | Enhanced refrigeration purge system | |
US20200149791A1 (en) | Low pressure refrigeration system with membrane purge | |
EP3483526B1 (en) | Low pressure refrigerant system | |
US11686515B2 (en) | Membrane purge system | |
US11913693B2 (en) | Enhanced refrigeration purge system | |
Vroon et al. | Transport properties of alkanes through ceramic thin zeolite MFI membranes | |
EP3483527A1 (en) | Refrigerant purge system with membrane protection | |
WO2012151429A1 (en) | Dehumidification, dehydration, or drying of uncompressed gases using water selective membranes and a portion of the retentate as a vacuum permeate sweep | |
JP2022009384A (en) | Systems and methods for purging chiller system | |
US10905997B2 (en) | Moisture separation system | |
US20210364202A1 (en) | Enhanced refrigeration purge system | |
EP3483530B1 (en) | Refrigeration purge system | |
EP4283222A1 (en) | Refrigeration system comprising a purge system and associated method of operating a purge system | |
EP4300010A1 (en) | Refrigeration system, the associated method of operating a purge system, and separator system | |
US11635240B2 (en) | Separator | |
US20180209670A1 (en) | Moisture separation system | |
WO2023181894A1 (en) | Membrane separation system and operation method for membrane separation system | |
WO2024081101A1 (en) | Low dew point air dehumidification system |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20191115 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20200116 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
GRAL | Information related to payment of fee for publishing/printing deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR3 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTC | Intention to grant announced (deleted) | ||
INTG | Intention to grant announced |
Effective date: 20200615 |
|
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTC | Intention to grant announced (deleted) | ||
INTG | Intention to grant announced |
Effective date: 20200915 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602018011295 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1350340 Country of ref document: AT Kind code of ref document: T Effective date: 20210115 Ref country code: CH Ref legal event code: NV Representative=s name: VALIPAT S.A. C/O BOVARD SA NEUCHATEL, CH |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210330 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210331 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1350340 Country of ref document: AT Kind code of ref document: T Effective date: 20201230 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210330 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2845218 Country of ref document: ES Kind code of ref document: T3 Effective date: 20210726 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210430 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210430 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602018011295 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 |
|
26N | No opposition filed |
Effective date: 20211001 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20211025 Year of fee payment: 4 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211108 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211108 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20221020 Year of fee payment: 5 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20221108 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20201230 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221130 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20181108 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20221108 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20231020 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20231201 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20231019 Year of fee payment: 6 Ref country code: FR Payment date: 20231019 Year of fee payment: 6 Ref country code: DE Payment date: 20231019 Year of fee payment: 6 |